Treatment of cellulosic fibrous materials



Patented Mar. 21, 1950 TREATMENT or QELLULOSIC FIBROUS MATERIALS Hendr k Ghr st aan a Upton Park, Cheste and Newton Wood Barritt, lnce, near Chester, England, assignors to Shell Bevelopment C0111- pany, San Francisco, Califa corporation pf Delaware No Draw s- Application December .19, 194 Sorial No. 635,066. In Great Britain December 15,

l This invention relates :to a process for the treatment of fibrous materials.

"It is an object .of the present invention to provide .an improved process for 'the wetting of fibrous -materials,*particularly those of a cellulosic nature such as cotton fibrous material, rayon, sisal and manila hemp.

According to the present invention, .a process is provided for the Wetting put of fibrous materials, particularly cellulosic material such as notton fibrous material, wherein the material is first treated with a .mono-oxy compound having h oxygen atom directly linked to a single carbon atom of a hydrocarbon. radical of eight to eleven carbon atoms ioll wed by .a trea ment W th an aqueous solution of an anion active detergent or wetting agent such as a water-soluble salt of an organic compound in which a hydrocarbon radical is linked with a carboxylated, sulfonated or sulfated solubiliz-ing group through an ester, amide or aryl linkage. Examples of such detergents which are commercially available are the salts of sulfonated or sulfatfid primary aliphatic alcohols (containing at least eight carbon atoms in the molecule) derived from fatty acid sources; the salts of sulfonated or suliated secondary aliphatic alcohols (containing at least eight carbon atoms in the molecule) derived from synthetic sources such as petroleum; salts of isethionio acid .101 o taurine condensation products with -fatty acids and salts of alkyl, aryl, .ara1kv a1ka y1, or beryl sulfonates. The .term keryl, as used herein, refers to the radical of an aliphatic hydrocarbon obtainable from kerosene. Examples of the carboxylated type of detergent are: fatty acid, naphthenioor rosin acidsoaps.

Preferably, the mono-oxy compound used in'the first step of the pro ess i analcoho most me era ly a ary o seconda y alcohol, orami tore thereof having an av rage hain length of ei to eleven arbon atoms pe mo ule, an preferably the anion active compound .used in the second step is a sulfated aliphatic alcohol detergent, most preferably a sodiumsalt of .a sulfated aliphatic alcohol containing from eight .toeighteen (and preferably sixteen to eighteen) carbon atoms .in the 311101801113, or a mixtureiof such salt-s such as is obtained by the sulfation of a mixture of olefins containin ;from six to eighteen carbon atoms in :the molecule. While :the :invention will 17 Claims. (01. 117-56) be particularly described with reference to the use in the first step of alcohols having an average chain length of eight to eleven, most preferably about nine, carbon atoms because of their out.- standing superiority, it is also applicable to other mono-oxy compounds wherein the oxygen atom is linked to a single carbon atom of a hydrocarbon radical of eight to eleven carbon atoms, such :as ketones and aldehydes.

It has already been proposed to improve the effective wetting power of alkyl sulfate salts :by the use of higher aliphatic alcohols. Thus, U. S. Patents 2,166,314 and 2,166,315 show that such an improvement may be obtained by employing an aqueous mixture of an alkyl sulfate salt and a higher alcohol, preferably an alcohol .corresponding to the alkyl sulfate salt used. An -im-, portant obiectof the present invention is to im.-,

prove upon :the prior methods of wett ng out fibrous material. More particularly, -it is an ob.- ject vof the present invention .to provide a more efiicient and more economical method for carrying out such wetting operations. is to materially reduce the wetting and treating time of fibrous materials in kier boiling, dyeing fibrous materials by pretreating the fibrous ma:v

teriaLl with an alcohol, ;or other :mQDO-Qxy cornpound wherein :the ,oi-l en atom is directly linked to is, single carbon atom of a.hydrocarbon radical having an average length in the compound or mixture thereof used .of eight to eleven carbon atoms, before contacting the fibers with the aqu ou -wet in solution. :Not on y a e the resu ts marke y better when thesame cry-co sounds are used n conjunction w th the aqueous wett ng olution, but also they reat y tsub ti with other m no-ros compounds o the same nera charact zliut ha in a difierau c ain en Wnile. as pr vi usly .-.indi oated, primar o sec- Another obje tondary aliphatic alcohols having a straight hydrocarbon chain of eight to eleven carbon atoms, such as n-octyl alcohol, n-nonyl alcohol, n-decyl alcohol, n-undecyl alcohol, Z-octanol, 4-octanol, 3-nonanol, Z-decanol, Z-undecanol, etc., are the preferred pretreating agents, branched chain aliphatic alcohols, for example, 2-methyl-4.-heptanol, 2,2,4-trimethyl-3-pentanol, 2,2,4-trimethyl-4-pentanol, 2,7-dimethyl-a-octanol, and the like, may also be used. Non-aliphatic alcohols can likewise be used as the pretreating agent in the process-3-pheny1 propanol, p-ethyl benzyl alcohol, tertiary butyl cyclohexanol, terpineoL-and the like being suitable, for example. Among the ketones which may be used are, for instance, methyl heptyl ketone, ethylisoamyl ketone, isopropyl n-butyl ketone, diisobutyl ketone, isobutyl n-amyl ketone, isopropyl cyclohexanone, acetophenone, etc. Aldehydes such as octyl aldehyde, decyl aldehyde, etc., are also useful in the process. Unsaturated alcohols, ketones and aldehydes corresponding to the foregoing "and like oompounds may likewise be used. Examples of such compounds are: 2-octene-4-ol, 6-methy1-4-heptene-2-ol, 2,6-dimethyl-2-heptene-7-ol, l-decene- 4-01, phorone, isophorone, cyclohexenylethanol' citronellol, and the like.

The mono-oxy compound may be used in pure or substantially pure form or as mixtures of one or more such individual compounds with or without other compounds which do not interfere with their desired action on the fibrous material being treated. Where mixtures of mono-oxy compounds of the indicated type are used, it is not essential that the individual components of the mixture used have hydrocarbon radicals of eight to eleven carbon atoms, provided the weighted average of such radicals falls in this range. In fact, an important feature of the invention is based upon the discovery that mixtures of a mono-oxy compound wherein the oxygen atom is attached to a single carbon atom of a hydrocarbon chain of less than eight carbon atoms with another mono-oxy compound having the oxygen atom attached to a single carbon atom of a hydrocarbon chain of more than eight carbon atoms, such that the average of the chain lenghts is eight to eleven carbon atoms, show a synergistic effect in that better results may be obtained with the mixture than with either component alone. This is the case, for example, with a mixture of equal parts of secondary hexyl alcohol and secondary decyl alcohol. Other mixtures which may be similarly used are, for instance, n-amyl alcohol with secondary dodecyl or lauryl alcohol, mesityl oxide with lauryl alcohol or ethyl-octyl ketone, etc. However, it is desirable that all components of the treating mixture be substantially waterinsoluble.

The chosen mono-oxy treating agent or mixture thereof may be applied to the. fibrous material in various ways. For instance, the material may be exposed to vapors of the chosen alcohol, aldehyde and/ or ketone until the surface of' the fibers is uniformly covered with an adsorbed layer thereof. Alternatively, the treating agent may be applied as a spray or mist to the fibrous material. Immersion of the fibers in the liquid treating agent or in a suitable non-aqueous solution thereof, preferably in a volatile solvent, e. g. in an ethereal solution, may likewise be used to deposit the desired surface film of alcohol, aldehyde and/or ketone thereon. Where solvents are used in depositing the treating agent, they may advantageously be recovered for reuse beper liter.

. Sec.

4 fore passing the pretreated fibrous material to the next step of the process, and in the interest of economy it is generally preferred to use liquid mono-oxy treating agents and to apply them directly to the fibers by diffusion or spreading, etc. without use of solvents.

The following tests show the advantages of the present invention.

EXAMPLE I Eight hanks of cotton yarn were placed in a tin above filter papers on which 1 cc. of a higher secondary alcohol or ketone had been dropped. The tin was closed and allowed to stand for five hours at the temperature stated in the following table. The wetting power was measured by the Draves test (cf. American Dyestuff Reporter (1939), 28, 425).

For the test of the wetting power solutions containing between 0.02% and 0.15% of a mixture of sodium salts of secondary aliphatic sulfated alcohols containing from sixteen to eighteen carbon atoms in the molecule, hereinafter referred to as "ester salts (obtained by sulfating a mixture of olefins containing from eight to eighteen carbon atoms in the molecule obtained by the cracking of parafiin wax) were used.

The wetting power is calculated in terms of the concentration of ester salt solution required to give a sinking time of 25 seconds, this concentration'being expressed relative to that of a standard sample of ester salt solution and standard untreated cotton which gave a sinking time of 25 seconds at an ester salt concentration of 0.8 gm. Thus, if the treated hank required an ester salt solution of only 0.2 gm. per liter to give a sinking time of 25 seconds, the Wetting power is said to be 400 relative to the standard sample which is assigned a wetting power of by definition The results are shown in Table I Table I Pretreatment Treating Agent Wetting Tempera- Power ture, O.

None 1 100 23 Sec. Hexyl alcohol 109 23 Sec. Heptyl alcohol. 320 28 Octyl alcohol 2,140 23 Sec. Nonyl alcoholl, 800 23 Sec. Decyl alcohol l, 120 23 Mixture of Sec. Undccyl and Dodecyl alcohols (1:1) 23 Mixture of Sec. Undecyl and Dodecyl alcohols (1:1) 300 40 Mixture of Sec. Hexyl and Sec. Decyl alcohols (1:1) 1, 900 23 Di-isobutyl ketone 880 20 Methyl-heptyl ketone -r l, 200 20 1 By definition.

EXAMPLE II The following results have been obtained with fatty acid soaps:

A domestic fatty acid soap no activating substance: Wetting power 55 at 40 C.

Same domestic fatty acid soap activation with mixed sec. octyl and nonyl alcohol: Wetting power 100 at 40 C.

Very much poorer results are obtained by mix-- ing the secondary alcohol with the aforesaid ester salts solutions as described in S. Patents 2,166,314 and 2,166,315. Table II shows the inefiiciency of such a procedure as comparedwith the process described in the present application.

Table II a Z Percent by Wetting Activating Substance wt. added .Power 190 91 101 4 115 Sec. Octyl alcohol 4 218 Mixture of Sec. Octyl and Nonyl alcohols. 4 253 Mixture of Sec. Decyl and Dodecyl alcohols 4 y 213 1 By definition.

The superiority of the process of the invention over even pretreatment with other polar compounds is shown by the following results obtained by following the same procedure as in Example I, using a treating temperature of about 23 C.:

It will thus be seen that the invention offers many advantages over prior art methods of wetting out fibrous materials, particularly with respect to economy in the use of treating agents. The process is capable of wide variation not only with regard to the mono-oxy compounds having the oxygen atom attached to a single carbon atom of a hydrocarbon radical of eight to eleven carbon atoms which may be used, but also in relation to the method of applying the film of pretreating agent to the fibers in the pretreatment step of the invention. It will therefore be understood that the process is not limited to the materials or methods described by way of illustration of the principles involved, nor by any theory proposed in explanation of the improved results attained.

We claim as our invention:

1. In a process of treating cellulosic fibrous material wherein the fibers are wetted with an aqueous solution of an anion-active wetting agent, the improvement which comprises the step of preliminarily treating the fibers with a substantially water-insoluble mono-oxy substituted hydrocarbon treating agent containing only carbon, hydrogen and oxygen in the molecule, said agent selected from the group consisting of the aliphatic alcohols, aliphatic ketones and aliphatic aldehydes having 8 to 11 carbon atoms per molecule and mixtures of at least two members of the group consisting of aliphatic alcohols, aliphatic ketones and aliphatic aldehydes having an average of 8 to 11 carbon atoms per molecule in the mixture to deposit on said fibers a surface film of said treating agent before carrying out said wetting of the fibrous material.

22-. in 1a proeessiof 'trea tingmellulosicl fibrous material wherein tthe fibers :a mewettedmiithan aqueous "solution of anmian ionaactive wetting agent, the improvement which comprises the of preliminarily treatin'g fibers with atleast one -al iphatic:.cseconuary mcno-hydroxy alcohol having a hydrocarbon-radical chaste-1'1 carbon atomsper molecule and containing ionlyvcarbon and hydrogen atomsand one oxygen atom in the molecule to deposit on "the fibers .a surta'ce film or said alcohol. before carrying 'outrsaidfwetting crane .fibrous'material. 1 In a process of itreait'irig cellulosic fibrous material wherein the fibers are wetted with aqueous solution of an anion-active wetting agent-the improvement which comprises the step of preliminai ilytreating-the fibers with at least one aliphatic mono-ketone having the ketooxygen atom directly attached to a hydrocarbon radical of 8 to 11 carbon atoms, said ketone containing only carbon and hydrogen atoms and one oxygen atom in the molecule to deposit on the fibers a surface film of said ketone before carrying out said wetting of the fibrous material.

4. In a process of treating cellulosic fibrous material wherein the fibers are wetted with an aqueous solution of an anion-active wetting agent, the improvement which comprises the step of preliminarily treating the fibers with a mixture of substantially water insoluble aliphatic monohydroxy alcohols containing only carbon and hydrogen atoms and one oxygen atom in the molecule, one of which alcohols contains less than 8 carbon atoms and another of which alcohols is of higher molecular weight such that the average number of carbon atoms per molecule of the mixture is 8 to 11 to deposit on the fibers a surface film of said alcohol mixture before carrying out said wetting of the fibrous material.

5. In a process of treating cotton fibers wherein the fibers are wetted with an aqueous solution of a sodium alkyl sulfate of 8 to 18 carbon atoms per molecule, the improvement which comprises the step of exposing the fibers to the vapors of a mixture of at least one substantially water insoluble aliphatic secondary mono-hydroxy alcohol having less than 8 carbon atoms per molecule together with at least one aliphatic secondary mono-hydroxy alcohol having more than 8 carbon atoms per molecule in proportions such that the average number of carbon atoms per molecule in the mixture is 8 to 11, said alcohols containing only carbon and hydrogen atoms and one oxygen atom in the molecule, whereby a film of said alcohols is deposited on the fibers before said wetting of the fibers is carried out.

6. In a process of treating cotton fibers wherein the fibers are wetted with an aqueous solution of a sodium alkyl sulfate of 8 to 18 carbon atoms per molecule, the improvement which comprises the step of exposing the fibers to the vapors of a mixture of at least one substantially water insoluble dialkyl ketone having less than 8 carbon atoms per molecule together with at least one dialkyl ketone having more than 8 carbon atoms per molecule in proportions such that the average number of carbon atoms per molecule in the mixture is 8 to 11, said ketones containing only carbon and hydrogen atoms and one oxygen atom in the molecule, whereby a film of said ketones is deposited on the fibers before said wetting of the fibers is carried out.

'7. A process of treating cellulosic fibrous material which comprises exposing said fibers to the vapors of a substantially water-insoluble monooxy substituted hydrocarbon treating agent containing only carbon, hydrogen and oxygen in the molecule, said agent selected from the group consisting of the aliphatic alcohols, aliphatic ketones and aliphatic aldehydes having 8 to 11 carbon atoms per molecule and mixtures of at least two members of the group consisting of aliphatic alcohols, aliphatic ketones and aliphatic aldehydes having an average of 8 to 11 carbon atoms per molecule in the mixture until a film of said agent is deposited on the fibers and subsequently contacting the thus treated fibers with an aqueous solution of an anion-active wetting agent.

HENDRIK CHRISTIAAN JANSEN.

NEWTON WOOD BARRITT.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

1. IN A PROCESS OF TREATING CELLULOSIC FIBROUS MATERIAL WHEREIN THE FIBERS ARE WETTED WITH AN AQUEOUS SOLUTION OF AN ANION-ACTIVE WETTING AGENT, THE IMPROVEMENT WHICH COMPRISES THE STEP OF PREMLIMINARILY TREATING THE FIBERS WITH A SUBSTANTIALLY WATER-INSOLUBLE MONO-OXY SUBSTITUTED BY HYDROCARBON TREATING AGENT CONTAINING ONLY CARBON, HYDROGEN AND OXYGEN IN THE MOLECULE, SAID AGENT SELECTED FROM THE GROUP CONSISTING OF THE ALIPHATE ALCOHOLS, ALIPHATIC KETONES AND ALIPHATIC ALDEHYDES HAVING 8 TO 11 CARBON ATOMS PER MOLECULE AND MIXTURES OF AT LEAST TWO MEMBERS OF THE GROUP CONSISTING OF ALIPHATIC ALCOHOLS, ALIPHATIC KETONES AND ALIPHATIC ALDEHYDES HAVING AN AVERAGE OF 8 TO 11 CARBON ATOMS PER MOLECULE IN THE MIXTURE TO DEPOSIT ON SAID FIBERS A SURFACE FILM OF SAID TREATING AGENT BEFORE CARRYING OUT SAID WETTING OF THE FIBROUS MATERIAL. 